Lubricating compositions



v lubricants, thus, preventing their breakdown 2:58.091 tunmcArnvocomosfnoiss William Cyril Webber, New Malden, Englaud, assignor to Shell Development Company,;Emeryville, Califi, a corporation of-Delaware No Drawing. Application- Apr l as, 1952,

g Serial No. 284,801 g e Claims Priority, app i a n; Gr tB i i I ctober,28, 1947.

8 Claims. (Cl. 252-493).

gears, as well as in metal fabrication, such as in cutting and drawing operations. Under such conditions of lubrication, the protective film-formed by the lubricant;. bee tween contacting surfaces, so as to prevent direct metalto me'tal Contact, breaks down or ruptures, thereby cans: ing seizure or even welding. of metal parts; this results in seriousdamage. tothe elements beinglubricated. To} overcome this serious weakness generally inherent in undoped lubricants, extreme pressure agents are usually addedgjthese agents form protective films between contactingsurfaces and possess,.among their'propertiesQthe function of imparting film strength and oiliness to=the and'ruptureunder the above-described lubricating conditions.

The action of extreme pressureragents. is largely .a physicochemicalphenomenon, and; this accounts .prima rily for theireifectiveness as extreme pressure agents:

These, agents, in addition to increasingthe film strength of .-,lub ricants, react with the contacting nietal'surfaces,. forming thereon a protective coating. or film of, great strength and thermal stability. This tenaciousl-y adher ing adsorbed protective .film notonly, reduces; friction between moving parts, such as those encountered ;in internal combustion engines, but alsoacts as an impennited States Patent 0 Patented .Aug. 7, 1956 2 in turn results in sticking and-fouling of movable en i e parts.

Numerous compounds and mixtures of compounds have been proposed and'tried as extreme pressureagents for lubricants, the. best .of. which have only, moderately improved. the ,extreme 1-pressure. propertie s of the lubrif cant, and even this generally at the expense of increased corrosiveness ,and; instability of the. lubricant. It is an object of the present invention to provide, an improved extreme: pressure type-lubricant. capableof effective lubricationunder high 'pre'ssures' at, elevated temperatures and adverse operating conditions. Still another objectof this invention is to provide an improved, stable, sludge, free, non-corrosive extreme pressure lubricant. Also,jit is an object .of-this invention to provide an improved extreme pressure lubricant by addition to any lubricating carrier onbase aminor amount of; a novel reaction product of this invention. Still another object is to form .animproved non-corrosive extreme pressurev additive, Other objects of this invention. will appear as the description proceeds.

' Broadly stated, this invention is directed to improved lubricants'containing a minor amount of a trihalomethyF ar'ylcarbinylphosphorus compound selected from the group consisting of phosphite, phosphate, and phospho- 7 time esters, and'al'so to the improving agents themselves.

meablefilmwhich prevents corrosive acidsand other contaminants from attacking the metal surfaces. To be effective, therefore, extreme pressure-agentsmust, to,-a degree, bereactive with-contacting surfaces and; form. thereon a protective film which prevents weldingof moving-pa'rts and aids lubrication. Since the reaction-isnon m'ally between the additives in the lubricantsand; the contacting surfaces at elevated temperatures of around about 500. C. and higher, the performance of.agiven lubricant must depend upon its composition, the com: position of the=coi1tacting surfaces being lubricated, and the conditions-to which the lubricant and thesurfaces are; subjected. 7

Although extreme pressureadditives, in order to be, eliective, should be reactive with contacting-surfaces,

this reactivity should notbe corrosive to the reactive; surface. This is generally a serious drawbackof known extreme pressure .,agents, for serious damagetto-metal surfaces, particularly in the caseof alloy bearings, might result. Such additives should also not tend to promote, x dation ,which gene a ly; p mp f ma on; of $9 1. sive acidic materials, sludge, lacquer and varnish; this The compounds are suitabl'y represented by the formula A= o),.;1 0. ,,-n. -R and the otherchalcogen analogues (S, Se, Te) thereof, wherein n, m and p are whole numbers from O'to l, with n -i-p being at. least 1, and n+mj+p being at least 2, and;A is a 't'rihalo'rnethylarylcarbinyl radical, e. g., l-t'ric'hloromethyl-l-phenylcarbinyl, and the Rs are in dependently selected hydrogen atoms or organic radicals which are residues of alcohols and phenols of theformula ROH, preferably hydrocarbyl radicals, especially alkyl radicals, of 1.to, 8 carbon'at'oms. The halogen atoms in A are. preferably selected from chlorine and bromine. e

The aryl radical may be nuclearly substituted with substituent groups such as lower alkyl, aryl, nitro, amino, hydroxyl, etc.,' particularly the para-nitro group.

.The compounds can be prepared by forming 2,2,2- ti ihalol arylethanol in accordance with the method of Chattaway and Muir (Journal of the Chemical Society 1934, p. 701') and reacting said compound with a-suite able phosphorus compound such as a phosphite triester;

. Asan illustrativeexample, the following method'was' employed in preparing diethyl (l phenyl-2,2;2-trichloroethyl) 'phosphite. f

About l'rnol of benzene and 3 mols ofchloralhydrate were reacted by the methodof Chattaway and Muir. so

. as to yield 2,2,2-trichl'or'o-l-phenylethanol About l 1nol of this material was treated with about 1 mol of triethyl phosphitefinbenzene using'trichloroacetic acid as a cata: lyst. After the reaction was complete, the benzene was removed by distillation and the unreacted trie'th'yl phosphite removed by distillationin vacuoat C. The final product was diethyl (1-pheny1-2,2;2-trih1oroethyl)- phos'phite'.

The following are other specific compounds exemplh fying'the compounds defined broadly above:-

Dibutyl (l-phenyl-2,2,2:trichloroethyl) phosphitev Dicresyl- (l phenyl-2,2,2-trichloroethyl) phosphite Dicyclohexyl (l-phenyl-2,2,2-trichloroethyl) phosphite Diethyl (l phenyl-Z,2,2-trichloroethyl.) phosphate Diethyl (l-phenyl-2,2,Z-tribromoethyl). phosphate" Et y ty phosphate l-phenyl,-2,2,2adichloromonobromoethyl) Ethyl (1-phenyl-2,2,2-trichloroethyl) acid phosphate Diethyl l-(4-nitrophenyl) -2,2,2-trichloroethyl] phosphite j Dicresyl [1-(4-chlorophenyl)-2,2,2-trichloroethyl] phosphite r Diethyl (1-phenyl-2,2,Z-trichloroethyl) thiophosphite Dicresyl ('1-phenyl-2,2,2-trichloroethyl) thiophosphite Diethyl (1-phenyl-2,2,2-trichloroethyl) selenophosphite Diethyl (1phenyl 2,2,2-trichloroethyl) telurophosphite Diethyl (1-phenyl-2,2,2-trichloroethyl) thiophosphate Diethyl (l-phenyl-2,2,Z-trichloroethyl) trithiophosphite Diethyl (1-phenyl-2,2,2-trichloroethyl) trithiophosphate Diethyl (1-phenyl-2,2,2,-trichloroethyl) triseleno phos phite Diethyl (l-phenyl-2,2,2-trichlorocthyl) dithiophosphite Dibutyl (1phenyl-2,2,Z-trichloroethyl) trithi ophosphite Of the extreme pressure additives within the ambit of this invention, those are preferred which are soluble in the lubricant to an extent suificient to give the compounded lubricant desired extreme pressure properties. It is possible, however, to produce excellent extremepressurelubricants by dispersing the additives in the lubricant in the form of a stable collodial suspension; thus, even those additives which are not readily soluble in the base lubricant can be employed. Suitable stabilizing and solubilizing agents may be added, such as long chain fatty alcohols having 8 to 20 carbon atoms, organic sulfonates, and the like.

In general, good results can be obtained by addition of the subject additives to a base lubricant in an amount of from a fraction of 1% up to 10%, the preferred range being from 0.1% to about by weight. w

The base for additives of this invention can be any natural or synthetic materials having lubricating properties. Thus, the base may be a hydrocarbon oilobtained from a paraffinic, naphthenic, Mid-Continent or Coastal stock and/or mixtures thereof. The viscosity of these oils may vary over a wide range such as from 100 SUS at 100 F. to 2000 SUS at 100 F. These oils may be refined by any of the well knownprocesses. The hydrocarbon oils may be blended with fixed oils, such as castor oil, lard oil, and the like, and/or with synthetic lubricants, such as polymerized olefins, copolymers of alkylene glycols and alkylene oxides organic esters (e. g., Z-ethyl hexyl sebacate, dioctyl phthalate, trioctyl phosphate), polymeric tetrahydrofuran, or polyalkyl silicone polymers, e. g., dimethyl silicone polymer, and the like. If desired, the synthetic lubricants may be used as the sole base lubricant or admixed with fixed oils and derivatives thereof.

General formulation of compositions of this invention can be represented by:

. Amount (per cent by weight) Organic phosphorus compound of this invention containing at least one CXs group Other additives, such as sulfonates, corrosion inhibitors, detergents, etc Base lubricant (natural and/or synthetic) c one oi-5 Balance Compositions of this invention were evaluated asextreme pressure agents by use of the Four-Ball Tester similar in principle to the Boerlage apparatus described in the magazine Engineering, volume 136, July 13, 1933. This apparatus comprises four steel balls arl fan'gt ed ina pyramid formation. The top ball is rotated by spin dles against the three bottom balls which are clamped in a stationary ball holder. The hallsare immersed in the compositions ,to be tested. Tests were run with undoped mineral oil and with 1% by weight of alubricant of this invention as indicated in the table below under various loads and the wear at these loads was measured. ;The fixed conditions under which the test were conducted are:

Test duration: 60 seconds Temperature: Ambient Hoffmann steel balls Lubricants of this invention were also tested on the I. A. E. 3% in". centres gear rig. The results obtained are summarized in the tablebelow:

I. A. E. 3% centres: 5 Pinion speed 2000 R. P. M.

Gears 1 tooth The gear material was En 39 and En 34 Base oil: mineral oil Four-Ball Additive Cone, Machine percent wt. Additive Wear Score Diem. at 140 kg. Load None 3.69 mm. 1% diethyl (1 -phony1*2,2,2-trichlorcethyl) 0101mm.

phosphlte.

I. A. E. 3%" Additive (30110., Additive Gear Rig percentwt. Scufling Load Obs.) 0.

None. 17. 0.6%.... diethyl (1-phenyl-2,2,2-trichloroethy1) 145.

phosphite. p

specific additives which can be used are oil-soluble de- Sn, Pb, Cr,.Mn, Fe, Ni, Co, etc.

tergents which include oil-soluble salts of various bases with detergent forming acids." Such bases include metal as well as=organic bases. Metallic bases include those of the alkali metals and of Cu, Mg, Ca, Sr, Ba, Zn, Cd, A1, Organic bases include various nitrogen bases as primary, secondary and tertiary amines and quaternary ammonium bases.

Examples of detergent forming acids are the various fatty acids of, say, 10 to 30 carbon atoms, wool fat acids,

.. parafiin wax acids (produced'by oxidation of parafiin wax), chlorinated fatty acids, resin acids, aromatic'carboxylic acids including aromatic fatty acids, aromatic hydroxy fatty acids, parafiinwax benzoic acids, various alkyl salicylic acids, phthalie acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkylphenol) sulfides and disulfides, methylene bis alkyl phenols; sulfonic acids such as may be produced by treatmentof alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid; sulfuric acid'inono-esters; phosm phoric, arsonic and antimony acid mono and diesters,

including the 'corresponding thiophosphoric, arsonic and antimony acidsj phosphoni-c acids and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thiophospliate diester; the alkaline earth diphenolates, specifically the calciumand barium salts of diphenol mono and poly sulfides.

Non-metallic detergents include compounds such as the phosphatidesysuch as lecithin and cephalin, certain fatty oils as rapeseed oils, vbltolized fatty or mineral oils and thelike.

An excellent metallic detergent for the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% sulfate ash. Also alkaline metal salts of alkyl phenol-aldehyde condensation reaction products are excellent detergents.

Antioxidants comprise several types, for example, alkyl phenols such as 2,4,6-trimethyl phenol, pentamethyl phenol, 2,4-dimethyl-6-tertiary-butyl phenol, 2,4-dimethyl- 6-octyl phenol, 2,6-ditertiary-butyl-4-methyl phenol, 2,4,6- tritertiary-butyl phenol and the like; amino phenols as benzyl amino phenols; amines such as dibutyl-phenylcne diamine, diphenyl amine, phenyl-beta-naphthylamine, phenyl-alpha-naphthylamine, dinaphthyl amine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to a nitrile, nitro or nitroso group (e. g., alpha cyano stearic acid).

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g., urethanes, allophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oilsoluble compounds.

Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.1 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with polyhalogen containing organic carbonyl compound and organic thiol, selenol and/or tellurol compound reaction products of this invention.

The novel phosphorus products of this invention, in addition to being excellent lubricating oil improving agents, are potent oxidation inhibitors for fuels, natural and synthetic rubber, wax coating compositions and other organic materials.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the broad scope of the disclosed invention.

This application is a continuation-in-part of my copending application Serial No. 55,043 filed October 18, 1948, which has matured into U. S. Patent 2,599,794.

I claim as my invention:

1. A lubricating composition consisting essentially of a major amount of a lubricating oil and a minor amount sulficient to impart extreme pressure properties thereto, of a dihydrocarbyl trihalomethyl-l-arylalkyl phosphite.

2. A composition of claim 1 but wherein the halo element is chlorine.

3. A composition of claim 2 but wherein the lubricating oil is a mineral lubricating oil.

4. A lubricating composition consisting essentially of a major amount of a mineral lubricating oil and a minor amount sufficient to impart extreme pressure properties thereto of a dialkyl trichloromethyl-l-aryl-alkyl phosphite.

5. A lubricating composition consisting essentially of a major amount of a mineral lubricating oil and a minor amount suflicient to impart extreme pressure properties thereto of a dialkyl trichloromethyl-l-phenyl-alkyl phosphite.

6. A lubricating composition consisting essentially of a major amount of a mineral lubricating oil and a minor amount sufficient to impart extreme pressure properties thereto of diethyl (1 phenyl 2,2,2 trichloroethyl) phosphite.

7. A lubricating composition consisting essentially of major amount of a mineral lubricating oil and a minor amount sufiicient to impart extreme pressure properties thereto of dibutyl (1 phenyl 2,2,2 trichloroethyl) phosphite.

8. A lubricating composition consisting essentially of a major amount of a mineral lubricating oil and a minor amount sufficient to impart extreme pressure properties thereto of dicresyl (1 phenyl 2,2,2 trichloroethyl) phosphite.

References Cited in the file of this patent UNITED STATES PATENTS 2,432,095 Frey Dec. 9, 1947 2,520,393 Fletcher Aug. 29, 1950 2,573,568 Harman et al Oct. 30, 1951 2,597,534 Schrader May 20, 1952 FOREIGN PATENTS 142,944 Australia Aug. 16, 1951 

1. A LUBRICATING COMPOSITION CONSISTING ESSENTIALLY OF A MAJOR AMOUNT OF A LUBRICATING OIL AND A MINOR AMOUNT SUFFICIENT TO IMPART EXTREME PRESSURE PROPERTIES THERETO OF A DIHYDROCARBYL TRIHALOMETHYL-1-ARYLALKYL PHOSPHITE. 